Dan Herring

Nitruración anódica por plasma de aleaciones de titanio

/ MEDICAL HEAT TREAT TECHNICAL, NITRIDING TECHNICAL CONTENT

En esta entrega de Martes Técnico, el Dr. Edward Rolinski y Dan Herring, conocidos respectivamente como “Doctor Glow” y The Heat Treat Doctor®, exploran cómo el nitrurado por plasma anódico para aleaciones de titanio evita los efectos dañinos del nitrurado catódico convencional mientras mejora la resistencia al desgaste, la resistencia a la corrosión y la confiabilidad de los componentes para aplicaciones aeroespaciales y médicas.

Este artículo informativo se publicó por primera vez en Heat Treat Today’s November 2025 Annual Vacuum Heat Treating print edition.

Para leer el artículo en inglés, haga clic aquí.

La nitruración tradicional por plasma/iónica es una tecnología consolidada. Sin embargo, presenta problemas que pueden solucionarse con el nuevo método de nitruración anódica por plasma. Este artículo presenta la idea de utilizar la nitruración anódica por plasma para titanio y aleaciones de titanio, evitando así los efectos perjudiciales de la nitruración catódica por plasma convencional. Descubra cómo este enfoque podría proporcionar capas más duras y sin defectos que mejoran el desgaste, la resistencia a la corrosión y la fiabilidad general de los componentes para piezas críticas de la industria aeroespacial y médica.

Qué es la nitruración anódica?

La nitruración anódica es un tipo de proceso de nitruración por plasma en el que las piezas tratadas se ubican en un potencial anódico (positivo) en lugar del potencial catódico (negativo) habitual. A diferencia de la nitruración por plasma convencional (descarga catódica), donde el componente se bombardea con iones positivos de alta energía, la nitruración anódica implica el bombardeo de electrones de baja energía sobre la superficie del componente.

La nitruración anódica es particularmente efectiva para materiales con una alta energía libre estándar negativa de formación de nitruros (p. ej., titanio, circonio), ya que ayuda a evitar o reducir el efecto de borde, un problema bien conocido en la nitruración catódica que provoca un bombardeo iónico desigual y endurecimiento en esquinas y bordes.

Antecedentes: Complejidades de la nitruración por plasma

La nitruración por plasma con descarga luminiscente se aplica a una amplia gama de materiales, como fundiciones, aceros al carbono, aceros inoxidables, níquel, aleaciones de titanio y pulvimetalurgia (Roliński, 2014). Los procesos de nitruración por plasma y nitrocarburación permiten la formación de capas superficiales con propiedades tribológicas superiores (Roliński, 2014). Sin embargo, la cobertura de las piezas con la descarga luminosa no siempre es uniforme, especialmente cuando se procesan cargas de geometría compleja (véase la Figura 1).

Figura 1. Pequeñas manchas oscuras (ver el área rodeada por el círculo) indican CDS durante la nitruración por plasma pulsado. Nota: Descarga luminiscente no uniforme en la parte superior de la pieza.
Source: Roliński and Herring
Figura 2. Carga de piezas de acero inoxidable tras la nitruración por plasma pulsado. Nota: Efecto de borde (EE) alrededor de la pieza.
Source: Roliński and Herring

La nitruración por plasma de baja descarga es un tratamiento termoquímico que utiliza partículas de alta energía. Los iones de nitrógeno u otras especies gaseosas se aceleran y ganan energía en el espacio oscuro de Crookes (CDS) alrededor de la pieza, que es el cátodo en una configuración de electrodos de corriente directa. Primero activan la superficie mediante pulverización catódica (sputtering) para eliminar cualquier óxido nativo presente. El tratamiento de pulverización catódica también genera una cantidad sustancial de partículas sólidas, generadas por la propia pieza, incluyendo átomos metálicos que flotan cerca de la superficie (Merlino y Goree, 2004; Roliński, 2005). En el procesamiento del titanio, por ejemplo, esto afecta tanto la adsorción como la difusión en la superficie, creando condiciones que degradan la calidad de la capa (Hubbard, et al., 2010). Se ha descrito un impacto negativo de este plasma “polvoriento” en la uniformidad de la capa nitrurada en piezas de geometría compleja (Ossowski et al., 2016).

Además, es bien sabido que durante la nitruración por plasma se observa el denominado efecto esquina/borde (EE), relacionado con la circulación desigual de estas partículas de polvo alrededor del cátodo (véase la Figura 2). En situaciones extremas, especialmente al tratar piezas de geometría compleja, el EE, causado por una distribución desigual del campo eléctrico en esquinas, cavidades, etc., da lugar a una distribución excesiva y desigual de estos depósitos de plasma (PD). De esta manera, el EE agrava el problema ya existente de la redeposición, lo que provoca la formación de diversos microdefectos y un espesor desigual de la capa nitrurada (Merlino y Goree, 2004; Roliński, 2005, 2024; Ossowski et al., 2016).

Figura 3. Componente de titanio después de nitruración gaseosa en amoníaco. Source: Roliński and Herring

La nitruración por plasma del titanio se realiza habitualmente a 680–1100 °C (1256–2012 °F). Entre los aspectos negativos del uso de la polarización catódica en titanio se incluyen el bombardeo de plasma/iónico, que provoca daños superficiales debido principalmente a micro-arcos y la contaminación de la superficie con los compuestos depositados, así como su distribución desigual debido al EE (Merlino y Goree, 2004; Roliński, 2005, 2014, 2024; Ossowski et al., 2016). Aunque el arco eléctrico se ha eliminado mediante la aplicación de técnicas de plasma pulsado, la pulverización catódica solo se puede controlar de forma limitada, especialmente cuando se nitruran piezas de geometría compleja. Por lo tanto, la nitruración gaseosa en amoníaco se ha utilizado ocasionalmente para endurecer piezas de titanio. Se produce un aspecto dorado resultante en la superficie que indica la presencia del nitruro TiN (véase la Figura 3).

Nitruración anódica de aleaciones de titanio

Se han realizado investigaciones sobre la nitruración anódica de aceros por plasma (Zlatanovic 1986; Michalski 1993; Kenĕz 2018). El amoníaco o las especies de nitrógeno activo generadas en el plasma pueden nitrurar el ánodo al igual que al cátodo. Las especies activas que causan la nitruración son átomos de nitrógeno activo y radicales NH altamente reactivos (NH*) formados en el plasma cercano. Los radicales NH (también conocidos como radicales imidógenos) son especies químicas con un enlace nitrógeno-hidrógeno junto con un electrón desapareado. En el caso del titanio, el hidrógeno debe excluirse en muchas situaciones, ya que reacciona con el titanio para formar hidruros estables que fragilizan el producto (Roliński, 2015).

La entalpía libre estándar de formación de nitruros de titanio tiene un valor negativo excepcionalmente alto, lo que significa que el nitruro de titanio se formará espontáneamente cuando el ánodo de titanio reaccione con nitrógeno excitado cercano (Roliński, 2015). Cambiar de polarización catódica a anódica de los componentes tratados ofrece varias ventajas notables. Una descarga luminosa en nitrógeno puro o argón genera únicamente iones positivos que se aceleran hacia el cátodo/pieza de trabajo. Dado que estas mezclas de gases carecen de iones negativos, solo los electrones de la luminiscencia anódica inciden en el ánodo/pieza de trabajo. Esto produce la activación de la superficie sin los efectos negativos de las colisiones de partículas más pesadas, como N₂+ (es decir, un ion molecular de nitrógeno con carga +1), lo que provoca una pulverización catódica excesiva. Al mismo tiempo, partículas de nitrógeno sin carga, como N₂* y N*, reaccionan con el ánodo por quimisorción en la superficie a una temperatura suficientemente alta, lo que finalmente conduce a la formación de la capa de difusión.

Se cree que el proceso de nitruración anódica puede tener efectos positivos en el tratamiento de piezas de precisión de titanio y otras aleaciones para su uso en las industrias aeroespacial y médica. Este método permitirá el tratamiento a la temperatura más baja posible gracias a la activación de la superficie con los electrones de la polarización anódica. La textura, la apariencia y una superficie sin defectos producirán una pieza superior y mejorarán el rendimiento de muchos de esos componentes. Esto será importante cuando la corrosión o las propiedades ópticas de la superficie sean importantes.

La nitruración anódica del titanio puede lograrse mediante un sistema convencional de nitruración por plasma, siempre que el ánodo central esté diseñado y ubicado adecuadamente. Este ánodo, o parte del mismo, debe estar hecho de titanio para evitar la evaporación y la transferencia de impurezas a las piezas.

Aplicaciones

Figura 4. Representación esquemática del aparato de nitruración por plasma anódico. Observe el color dorado característico del nitruro de titanio (TiN) presente en los accesorios y piezas de titanio, todos identificados como “ánodo”. Source: Roliński and Herring

Las aleaciones de titanio son populares en ortopedia debido a su elasticidad, resistencia y biocompatibilidad similares a las del hueso (Roliński 2015; Froes 2015). Los procesos de ingeniería de superficies, como la nitruración anódica, pueden desempeñar un papel importante a la hora de prolongar el rendimiento de los dispositivos ortopédicos varias veces más allá de su vida útil normal.

Los materiales intermetálicos superelásticos, como el 60NiTi, se utilizan en elementos de rodamientos debido a su resistencia a la corrosión y al impacto (Pohrelyuk et al., 2015; Corte et al., 2015). Suelen ser propensos a la degradación por fatiga de contacto rodante (RCF). Cualquier defecto superficial presente en estos componentes, como la concentración local de impurezas o microfisuras, provocará un fallo prematuro. La nitruración por plasma anódico puede utilizarse para endurecer las superficies de los componentes de rodamientos fabricados con estas aleaciones, formando una capa dura y sin defectos, lo que puede mejorar sus propiedades ante el RCF.

Se espera que las piezas de titanio u otras aleaciones con la superficie sometida a nitruración anódica estén libres de micro-defectos, lo que permite su amplia aplicación en el campo médico, la industria aeroespacial y los dispositivos ópticos y semiconductores.

Referencias

Corte, Ch. Della, M. K. Stanford, and T. R. Jett. 2015. “Rolling Contact Fatigue of Superelastic Intermetallic Materials (SIM) for Use as Resilient Corrosion Resistant Bearings.” Tribology Letters 26: 1–10.

Froes, F. H., ed. 2015. Titanium: Physical Metallurgy, Processing and Applications. Materials Park, OH: ASM International.

Hubbard, P., J. G. Partridge, E. D. Doyle, D. G. McCulloch, M. B. Taylor, and S. J. Dowey. 2010. “Investigation of Mass Transfer within an Industrial Plasma Nitriding System I: The Role of Surface Deposits.” Surface and Coatings Technology 204: 1145–50.

Kenĕz, L., N. Kutasi, E. Filep, L. Jakab-Furkas, and L. Ferencz. 2018. “Anodic Plasma Nitriding in Hollow Cathode (HCAPN).” HTM Journal of Heat Treatment and Materials 73 (2): 96–105.

Merlino, R. L., and J. A. Goree. 2004. “Dusty Plasmas in the Laboratory, Industry, and Space.” Physics Today, July, 32–38.

Michalski, J. 1993. “Ion Nitriding of Armco Iron in Various Glow Discharge Regions.” Surface and Coatings Technology 59 (1–3): 321–24. https://doi.org/10.1016/0257-8972(93)90105-W.

Ossowski, Maciej, Tomasz Borowski, Michal Tarnowski, and Tadeusz Wierzon. 2016. “Cathodic Cage Plasma Nitriding of Ti6Al4V.” Materials Science (Medžiagotyra) 22 (1).

Pohrelyuk, I., V. Fedirko, O. Tkachuk, and R. Poskurnyak. 2015. “Corrosion Resistance of Ti-6Al-4V Alloy with Oxidized Nitride Coatings in Ringer’s Solution.” Inzynieria Powierzchni (Surface Engineering) 1: 38–46.

Roliński, E. 2014. “Plasma Assisted Nitriding and Nitrocarburizing of Steel and Other Ferrous Alloys.” In Thermochemical Surface Engineering of Steels, edited by E. J. Mittemeijer and M. A. J. Somers, 413–57. Woodhead Publishing Series in Metals and Surface Engineering 62. Cambridge, UK; Waltham, MA; and Kidlington, UK: Woodhead Publishing.

Roliński, E. 2015. “Nitriding of Titanium Alloys.” In ASM Handbook, Volume 4E: Heat Treating of Nonferrous Alloys, edited by G. E. Totten and D. S. McKenzie, 604–21. Materials Park, OH: ASM International.

Roliński, Edward. 2024. “Practical Aspects of Sputtering and Its Role in Industrial Plasma Nitriding.” In ASM Handbook Online, Volume 5: Surface Engineering. Materials Park, OH: ASM International. https://doi.org/10.31399/asm.hb.v5.a0007039.

Roliński, E., J. Arner, and G. Sharp. 2005. “Negative Effects of Reactive Sputtering in an Industrial Plasma Nitriding.” Journal of Materials Engineering and Performance 14 (3): 343–50.

Zlatanovic, M., A. Kunosic, and B. Tomčik. 1986. “New Development in Anode Plasma Nitriding.” In Proceedings of the International Conference on Ion Nitriding, Cleveland, OH, September 15–17, edited by T. Spalvins, 47–51. Cleveland, OH: NASA Lewis Research Center.

About The Authors:

Dr. Edward Rolinski
“Doctor Glow”

El Dr. Edward Rolinski, conocido afectuosamente como “Doctor Glow”, es un distinguido científico sénior que ha liderado la investigación sobre nitruración por plasma/iones desde la década de 1970. Posee títulos avanzados en tecnología de fabricación y metalurgia, incluyendo un doctorado en Ciencias. Se ha centrado en los procesos de nitruración por plasma, especialmente en aleaciones de titanio y pulvimetalurgia. A lo largo de su carrera, el Dr. Rolinski ha sido autor de numerosos capítulos y artículos técnicos influyentes, incluyendo para ASTM International y el Manual ASM, y es un prolífico colaborador en publicaciones del sector. Tras décadas de liderazgo e innovación en ingeniería de superficies y tratamiento térmico, ahora es un consultor en la industria del tratamiento térmico.

Dan Herring
(The Heat Treat Doctor®)
The HERRING GROUP, Inc.

Dan Herring, conocido como The Heat Treat Doctor®, lleva más de 50 años en la industria. Dedicó sus primeros 25 años al tratamiento térmico antes de fundar su empresa de consultoría, The HERRING GROUP, en 1995. Su amplia experiencia en el campo abarca la ciencia de los materiales, la ingeniería, la metalurgia, el diseño de equipos, la especialización en procesos y aplicaciones, y la investigación de nuevos productos. Es autor de seis libros y más de 700 artículos técnicos.

Para más información: Contacte con Dan en dherring@heat-treat-doctor.com.

Nitruración anódica por plasma de aleaciones de titanio Read More »

Anodic Plasma Nitriding of Titanium Alloys

/ MEDICAL HEAT TREAT TECHNICAL, NITRIDING TECHNICAL CONTENT

In this Technical Tuesday installment, Dr. Edward Rolinski and Dan Herring, respectively known as “Doctor Glow” and The Heat Treat Doctor®, explore how anodic plasma nitriding for titanium alloys avoids the damaging effects of conventional cathodic nitriding while improving wear resistance, corrosion resistance, and component reliability for aerospace and medical applications.

This informative piece was first released in Heat Treat Today’s November 2025 Annual Vacuum Heat Treating print edition.

To read the article in Spanish, click here.

Traditional plasma/ion nitriding is a well-established technology. However, it has issues that can be overcome by the newer anodic plasma nitriding method. This article introduces the idea of using anodic plasma nitriding for titanium and titanium alloys to avoid the damaging effect of conventional (cathodic) plasma nitriding. Read how this approach could provide harder, defect-free layers that improve wear, corrosion resistance, and overall component reliability for aerospace and medical critical parts.

What Is Anodic Nitriding?

Anodic nitriding is a type of plasma nitriding process in which the component parts being treated are placed at an anodic (positive) potential instead of the usual cathodic (negative) potential. Unlike conventional plasma (cathodic glow discharge) nitriding, where the component is bombarded by high-energy positive ions, anodic nitriding involves low-energy electron bombardment of the component’s surface.

Anodic nitriding is particularly effective for materials with very high negative Standard Free Energy of nitride formation (e.g., titanium, zirconium) as it helps avoid or reduce the edge effect, a well-known problem in cathodic nitriding that leads to uneven ion bombardment and hardening on corners and edges.

Background: Plasma Nitriding Complexities

Glow-discharge plasma nitriding is applied to a wide range of materials, including cast irons, carbon steels, stainless steels, nickel, titanium alloys, and powder metal (Roliński 2014). The plasma nitriding and nitrocarburizing processes allow for the formation of surface layers known to have superior tribological properties (Roliński 2014). However, coverage of the parts with the glow discharge is not always uniform, especially when complex geometry loads are processed (see Figure 1).

Figure 1. Small dark spots (see circled area) indicate CDS during pulse plasma nitriding. Note: Non-uniform glow discharge at the top of the part.
Source: Roliński and Herring
Figure 2. Load of stainless-steel parts after pulse plasma nitriding. Note: Edge effect (EE) around the part.
Source: Roliński and Herring

Glow-discharge plasma nitriding is a thermochemical treatment involving high-energy particles. Ions of nitrogen or other gas species accelerate and gain energy in the cathodic dark space (CDS) around the workpiece — which is the cathode in a direct current electrode setup. They activate the surface first by sputtering to remove any native oxides present. The sputtering treatment also results in the generation of a substantial quantity of solid particles, generated from the part itself, including metal atoms that levitate near the surface of the part (Merlino and Goree 2004; Roliński 2005). In processing titanium, for example, this affects both adsorption and diffusion at the surface creating conditions that degrade layer quality (Hubbard, et al. 2010). A negative impact of this “dusty” plasma on the uniformity of the nitrided layer in complex-geometry workpieces has been reported (Ossowski, et al. 2016).

In addition, it is well known that there is a so-called corner/edge effect (EE) observed during plasma nitriding related to uneven circulation of these dust particles around the cathode (see Figure 2). In extreme situations, especially when complex geometry parts are treated, the EE caused by a non-uniform distribution of the electric field on corners, cavities, etc., results in excessive and non-uniform distribution of these plasma deposits (PD). In this way, the EE amplifies the already-present problem of redeposition, leading to the formation of various microdefects and uneven nitrided layer thickness (Merlino and Goree 2004; Roliński 2005, 2024; Ossowski, et al. 2016).

Figure 3. Titanium component after gas nitriding in ammonia | Source: Roliński and Herring

Plasma nitriding of titanium is usually performed at 680–1100°C (1256–2012°F). Negative aspects of using cathodic polarization on titanium include plasma/ion bombardment resulting in surface damage due primarily to micro arcing and contamination of the surface with the deposited compounds and their uneven distribution due to EE (Merlino and Goree 2004; Roliński 2005, 2014, 2024; Ossowski, et al. 2016). Although arcing has been eliminated by applying pulse plasma techniques, sputtering can only be controlled in a limited way, especially when complex geometry parts are nitrided. Therefore, gas nitriding in ammonia has been used occasionally for hardening titanium parts. A resulting golden appearance representing the presence of TiN nitride is produced on the surface (see Figure 3).

Anodic Nitriding of Titanium Alloys

Research has been conducted on anodic plasma nitriding of steels (Zlatanovic 1986; Michalski 1993; Kenĕz 2018). Ammonia or active nitrogen species generated in the plasma can nitride the anode just as they do the cathode. The active species causing nitriding are active nitrogen atoms and highly reactive NH radicals (NH*) formed in near plasma. NH radicals (aka imidogen radicals) are chemical species with a nitrogen-hydrogen bond along with an unpaired electron. For titanium, hydrogen must be excluded in many situations because it reacts with titanium to form stable hydrides that embrittle the product (Roliński 2015).

The standard free enthalpy of formation of titanium nitrides has an exceptionally large negative value, which means that titanium nitride will form in a spontaneous way when the titanium anode reacts with excited nitrogen nearby (Roliński 2015). Switching the treated components from cathodic to anodic polarization offers several notable advantages. A glow discharge in pure nitrogen or argon generates only positive ions that are accelerated toward the cathode/workpiece. Because these gas mixtures lack negative ions, only electrons from the anodic glow strike the anode/workpiece. This results in activation of the surface without negative aspects of the collisions of the heavier particles, such as N2+ (i.e., a nitrogen molecular ion with a +1 charge), causing excessive sputtering. At the same time, charge-free particles of nitrogen, such as N2* and N*, react with the anode and are chemisorbed at the surface at sufficiently high temperature, leading eventually to formation of the diffusion layer.

It is believed that the anodic-nitriding process may have positive effects in treating precision parts made of titanium and other alloys for use in both the aerospace and medical industries. This method will allow treatment at the lowest possible temperature due to activation of the surface with the electrons from anodic polarization. The texture, appearance, and defect-free surface will produce a superior part and will enhance the performance of many of those components. This will be important when corrosion or optical properties of the surface play a significant role.

Anodic nitriding of titanium can be accomplished within a conventional plasma nitriding system, provided that the central anode is appropriately designed and positioned. This anode or portion of it must be made of titanium to prevent evaporation and transfer of any impurities to the parts.

Applications

Figure 4. Schematic representation of the anodic plasma nitriding apparatus. Note the gold color characteristic for titanium nitride TiN present on the titanium fixturing and parts, all being identified as “anode.” | Source: Roliński and Herring

Titanium alloys are popular in orthopedics due to their bone-like elasticity, strength, and biocompatibility (Roliński 2015; Froes 2015). Surface engineering processes like anodic nitriding can play a significant role in extending the performance of orthopedic devices several times beyond their normal life expectancy.

Super elastic intermetallic materials, such as 60NiTi, are used in rolling element bearings due to their resistance to corrosion and shock (Pohrelyuk, et al. 2015; Corte, et al. 2015). They are typically prone to rolling contact fatigue (RCF) degradation. Any surface defects present in those components, such as local concentration of impurities or micro-cracks, will result in premature failure. Anodic plasma nitriding can be potentially used to harden the surfaces of bearing components made from these alloys by forming a hard, defect-free layer, which may improve their RCF properties.

It is expected that parts made of titanium or other alloys with the smooth surface subjected to the anodic nitriding will be microdefects-free, enabling their broad applications in medical field, aerospace industry, and optical and semiconductor devices.

References

Corte, Ch. Della, M. K. Stanford, and T. R. Jett. 2015. “Rolling Contact Fatigue of Superelastic Intermetallic Materials (SIM) for Use as Resilient Corrosion Resistant Bearings.” Tribology Letters 26: 1–10.

Froes, F. H., ed. 2015. Titanium: Physical Metallurgy, Processing and Applications. Materials Park, OH: ASM International.

Hubbard, P., J. G. Partridge, E. D. Doyle, D. G. McCulloch, M. B. Taylor, and S. J. Dowey. 2010. “Investigation of Mass Transfer within an Industrial Plasma Nitriding System I: The Role of Surface Deposits.” Surface and Coatings Technology 204: 1145–50.

Kenĕz, L., N. Kutasi, E. Filep, L. Jakab-Furkas, and L. Ferencz. 2018. “Anodic Plasma Nitriding in Hollow Cathode (HCAPN).” HTM Journal of Heat Treatment and Materials 73 (2): 96–105.

Merlino, R. L., and J. A. Goree. 2004. “Dusty Plasmas in the Laboratory, Industry, and Space.” Physics Today, July, 32–38.

Michalski, J. 1993. “Ion Nitriding of Armco Iron in Various Glow Discharge Regions.” Surface and Coatings Technology 59 (1–3): 321–24. https://doi.org/10.1016/0257-8972(93)90105-W.

Ossowski, Maciej, Tomasz Borowski, Michal Tarnowski, and Tadeusz Wierzon. 2016. “Cathodic Cage Plasma Nitriding of Ti6Al4V.” Materials Science (Medžiagotyra) 22 (1).

Pohrelyuk, I., V. Fedirko, O. Tkachuk, and R. Poskurnyak. 2015. “Corrosion Resistance of Ti-6Al-4V Alloy with Oxidized Nitride Coatings in Ringer’s Solution.” Inzynieria Powierzchni (Surface Engineering) 1: 38–46.

Roliński, E. 2014. “Plasma Assisted Nitriding and Nitrocarburizing of Steel and Other Ferrous Alloys.” In Thermochemical Surface Engineering of Steels, edited by E. J. Mittemeijer and M. A. J. Somers, 413–57. Woodhead Publishing Series in Metals and Surface Engineering 62. Cambridge, UK; Waltham, MA; and Kidlington, UK: Woodhead Publishing.

Roliński, E. 2015. “Nitriding of Titanium Alloys.” In ASM Handbook, Volume 4E: Heat Treating of Nonferrous Alloys, edited by G. E. Totten and D. S. McKenzie, 604–21. Materials Park, OH: ASM International.

Roliński, Edward. 2024. “Practical Aspects of Sputtering and Its Role in Industrial Plasma Nitriding.” In ASM Handbook Online, Volume 5: Surface Engineering. Materials Park, OH: ASM International. https://doi.org/10.31399/asm.hb.v5.a0007039.

Roliński, E., J. Arner, and G. Sharp. 2005. “Negative Effects of Reactive Sputtering in an Industrial Plasma Nitriding.” Journal of Materials Engineering and Performance 14 (3): 343–50.

Zlatanovic, M., A. Kunosic, and B. Tomčik. 1986. “New Development in Anode Plasma Nitriding.” In Proceedings of the International Conference on Ion Nitriding, Cleveland, OH, September 15–17, edited by T. Spalvins, 47–51. Cleveland, OH: NASA Lewis Research Center.

About The Authors:

Dr. Edward Rolinski
“Doctor Glow”

Dr. Edward Rolinski, affectionately known as “Doctor Glow,” is a distinguished senior scientist having spearheaded research on plasma/ion nitriding since the 1970s. He holds advanced degrees in manufacturing technology and metallurgy, including a PhD and Doctor of Science. His focus has been on plasma nitriding processes, especially involving titanium alloys and powder metallurgy. Over his career, Dr. Rolinski authored numerous influential technical chapters and articles, including for ASTM International and the ASM Handbook, and is a prolific contributor to industry publications. After decades of leadership and innovation in surface engineering and heat treating, he is now a consultant in the heat-treating industry.

Dan Herring
(The Heat Treat Doctor®)
The HERRING GROUP, Inc.

Dan Herring, who is most well known as The Heat Treat Doctor®, has been in the industry for over 50 years. He spent the first 25 years in heat treating prior to launching his consulting business, The HERRING GROUP, in 1995. His vast experience in the field includes materials science, engineering, metallurgy, equipment design, process and application specialist, and new product research. He is the author of six books and over 700 technical articles.

For more information: Contact Dan at dherring@heat-treat-doctor.com.

Anodic Plasma Nitriding of Titanium Alloys Read More »

Ask The Heat Treat Doctor®: What Masks the Steel’s Surface in Case Hardening?

/ HARDENING TECHNICAL CONTENT, MANUFACTURING HEAT TREAT TECH

Ask The Heat Treat Doctor® has returned to bring sage advice to Heat Treat Today readers and to answer your questions about heat treating, brazing, sintering, and other types of thermal treatments as well as questions on metallurgy, equipment, and process-related issues.

This informative piece was first released in Heat Treat Today’s November 2025 Annual Vacuum Heat Treating print edition.

Case depth, case uniformity, and final mechanical (as well as other) properties rely not only on controlling both equipment and process variability during heat treatment, but on having clean, properly prepared part surfaces prior to and during heat treating. Expert Dan Herring encourages to learn more below.

Case hardening is a thermochemical surface treatment process designed to add a particular element or combination of elements to a material such as steel. Familiar examples include carbon (carburizing); carbon and nitrogen (carbonitriding); boron (boriding); nitrogen (nitriding); and nitrogen and carbon (nitrocarburizing — ferritic or austenitic). These processes are typically designed to increase the near surface hardness of steel after quenching.

However, various problems can arise due to either the materials or the manufacturing methods employed prior to or during heat treating that will retard or prevent absorption and/or diffusion of the desired element(s) during heat treating. Some of the metallurgical consequences can include:

  • Shallow or uneven case depths
  • Surface oxidation
  • Intergranular oxidation or decarburization
  • High levels of retained austenite
  • Soft spots due to incomplete hardening

Machine-Induced Surface Conditions

Improper machining prior to case hardening can compromise surface integrity. Tooling choices, improperly maintained equipment, inadequate operator training, and even environmental factors can contribute to a variety of issues.

While machining problems occur frequently, they are mostly preventable. Attention to part surface condition, cleanliness, and mechanical integrity is essential before heat treating. Training, standardizing machining protocols, planned preventative maintenance programs, and part inspection prior to heat treating will help avoid these issues. Consult Table A for further details on how the causes and effects of undesirable machine-induced surface conditions can be solved.

Splatter of Stop-off Paints on Unintended Areas

A material that masks the surface of steel and delays or prevents case hardening is called a stop-off or maskant. These materials are applied to specific areas of a steel part to prevent the diffusion of hardening elements (like carbon or nitrogen) into the surface during case hardening processes, such as carburizing, nitriding, or carbonitriding. (See Table B.)

Enriching Gas Additions (Sooting)

During the carburizing or carbonitriding process, it is not uncommon to develop a layer of soot on the surface of the parts, especially if the enriching gas additions begin before the entire load is uniformly up to temperature. In some instances, the amount of soot formation is such that the case depth or uniformity is affected. This is often difficult to diagnose, as the soot layer “washes off” during quenching in a liquid, and the part surfaces come out of the furnace looking reasonably clean.

The use of scrap in steelmaking, especially for low alloy case hardening steels can lead to a relatively high level of impurities and tramp elements. At high temperatures these impurities tend to segregate at grain boundaries and migrate toward the surface. This type of segregation can retard case hardening by impeding element (e.g., carbon) transfer. For example, the effects of tin (Sn) and antimony (Sb) on the kinetics of carburization are particularly problematic (Figure 1).

The effect of tramp elements on retardation of carburization can be expressed in the following order (Andreas, et al. 1996), namely Sb > Sn > P > Cu > Pb. To see the effect of one such element, the carbon transfer coefficient (ß) for typical commercial steels is shown as a function of antimony (Sb) content (Figure 2).

In Summary

These are a few of the many causes delaying or preventing case hardening from being effective. There are many others, including alkaline cleaning compounds (in too high a concentration) and even phosphate and other drawing lubricants used in the manufacture of fasteners. Inspection and cleaning of the part surface prior to case hardening will avoid many of these issues. Reviewing material certification sheets for elements known to interfere with case hardening is also an effective way to anticipate problems with case hardening.

References

Herring, Daniel H. 2014. Atmosphere Heat Treatment, Volume 1. Troy, MI: BNP Media.

Herring, Daniel H. 2015. Atmosphere Heat Treatment, Volume 2. Troy, MI: BNP Media.

Ruck, Andreas, Monceau, Daniel, and Grabke, Hans Jürgen. 1996. “Effects of Tramp Elements Cu, P, Pb, Sb, and Sn on the Kinetics of Carburization of Case Hardened Steels.” Steel Research 67 (6): 242–48.

About the Author

Dan Herring
“The Heat Treat Doctor”
The HERRING GROUP, Inc.

Dan Herring has been in the industry for over 50 years and has gained vast experience in fields that include materials science, engineering, metallurgy, new product research, and many other areas. He is the author of six books and over 700 technical articles.

For more information: Contact Dan at dherring@heat-treat-doctor.com.

For more information about Dan’s books: see his page at the Heat Treat Store.

Ask The Heat Treat Doctor®: What Masks the Steel’s Surface in Case Hardening? Read More »

What Is Hydrogen Embrittlement? Part 2

/ BRAZING TECHNICAL CONTENT, Manufacturing Heat Treat Technical Content

Ask The Heat Treat Doctor® has returned to bring sage advice to Heat Treat Today readers and to answer your questions about heat treating, brazing, sintering, and other types of thermal treatments as well as questions on metallurgy, equipment, and process-related issues.

This informative piece was first released in Heat Treat Today’s October 2025 Ferrous & Nonferrous Heat Treatments/Mill Processing print edition.

In today’s Technical Tuesday, Dan Herring continues his exploration of what hydrogen embrittlement is by contrasting it with other forms of embrittlement. Learn how to identify these various forms of brittle intergranular failure below!

We continue our discussion from last month concerning hydrogen-assisted cracking (aka hydrogen embrittlement) by looking at closely related phenomena, often mistaken for hydrogen embrittlement. Let’s learn more.

As a brief recap of what we discussed last month, the severity and mode of the hydrogen damage depends on:

  • Source of hydrogen — external (gaseous) or internal (dissolved)
  • Exposure time
  • Temperature and pressure
  • Level of residual and applied stresses
  • Type of alloy and its production method
  • Method of heat treatment
  • Treatment of exposed surfaces (barrier layers, e.g., oxide layers as hydrogen permeation barriers on metals)
  • Final treatment of the metal surface (e.g., galvanic nickel plating)
  • Presence of chemicals that may react with metals (e.g. acidic solutions)
  • Number of discontinuities in the metal

There are, however, several other embrittlement mechanisms that are often mistaken for hydrogen embrittlement and we will explore these here.

Quench Embrittlement

Contact us with your Reader Feedback!

Many high hardenability steels (e.g., 4140, 4340, 52100) are susceptible to a form of brittle intergranular failure from a phenomenon known as quench embrittlement. Under tensile or bending stress, higher carbon steels are susceptible to intergranular fracture in both the as-quenched condition and/or after low temperature tempering — generally considered “safe” from traditional embrittlement. A transition from ductile to intergranular fracture in martensitic steels having greater than 0.5% C can be embrittled even when tempered at low temperatures.

This phenomenon is different from tempered martensite embrittlement (TME) or temper embrittlement (TE), as explained below, as embrittlement occurs before tempering. The issue is exacerbated by the presence of certain embrittling elements (e.g., P, S, As, Sb, Sn, Pb) solely or when their combination reaches a high enough percentage (typically, 0.10%).

Temper Embrittlement

In broad based terms, TE involves a reduction in the normal ductility of a metal due to a physical or chemical change. TE is characterized by reduced impact toughness and occurs in certain quenched and tempered steels and even in ductile irons with susceptible compositions. This form of embrittlement does not typically affect room temperature tensile properties but causes significant reductions in impact toughness and fatigue performance. Although normally associated with tempered martensite, it can also occur if the matrix is tempered to the fully ferritic condition.

Types of Temper Embrittlement

When tempering steel, several types of embrittlement must be avoided. The first type, TME, is an irreversible phenomenon that can occur within 200−400°C (390−750°F). Years ago, it was called “blue brittleness” for the steel’s surface oxidation appearance, but this term is misleading since it can occur at temperatures below the onset of a blue coloration on steel.

Figure 1. Fracture modes in hardened steels

The second type is TE, a reversible phenomenon that occurs when steels are heated in and/or slow cooled through the temperature range of 375−575°C (705−1070°F).

Why Does it Happen?

TME and TE are examples of intergranular embrittlement. A common factor in such failures is the presence of elements that segregate to the grain boundaries. The chemical reaction rate or kinetics of segregation are such that they exhibit “C” curve behavior in the 350−550°C (660−1020°F) range; in other words, segregation does not occur uniformly. Both types of embrittlement are in part related to grain-boundary segregation of impurity elements (e.g., As, P, Sb, Sn), and both develop during thermal processing after austenitizing and quenching to martensite, usually indicated by an upward shift in ductile-to-brittle transition temperature.

TME is thought to result from the combined effects of cementite precipitation on prior-austenite grain boundaries or interlath boundaries and the segregation of impurities at prior-austenite grain boundaries. By contrast, TE is thought to be caused by the formation of carbides on decomposition of martensite, in particular, precipitation of carbides in the form of films at grain boundaries. At higher temperatures of tempering, this film disappears and cannot be restored on repeated heating at 250−400°C (480−750°F).

Which Steels Are Affected?

All steels are susceptible, so the real question becomes how susceptible and what factors affect that susceptibility. For example, while plain carbon steels may contain some of the same impurity elements that will cause the embrittlement phenomenon to occur in other steels, the segregation of these elements is often enhanced by or caused by the presence of other alloying elements in substantial quantities. As a result, alloy steels, in general, have more susceptibility than carbon steels.

It is important to understand that the degree of embrittlement is affected by the prior austenite grain size and hardness. So, if we are dealing with a fine-grained plain carbon steel of low hardness, it may not experience embrittlement symptoms despite its phosphorous content, whereas a more highly alloyed Cr-Ni steel used at higher hardness is more susceptible to its impurity content.

Widely used alloying elements, such as chromium, nickel, and manganese, tend to promote TE with the highest embrittlement effect observed in Cr-Ni and Cr-Mn steels. Small additions of molybdenum (0.2-0.3%) can diminish TE, while greater additions enhance the effect. TE can be prevented by keeping silicon and phosphorus levels as low as possible, adding up to 0.15% molybdenum and avoiding the embrittlement heat treating conditions.

Susceptibility also depends on impurity control and here is where the steelmaking process is critical. For example, in plain carbon and Cr-Mo steels (those with no Ni) where phosphorous is the most impactful embrittlement element, the percentage can be controlled by the steelmaking process. In steels that contain significant amounts of nickel, antimony and tin are more potent embrittlement elements. Phosphorous has an effect but not as large as it has in plain carbon and Cr-Mo steels. It should be noted, however, that antimony and tin in plain carbon steels can cause other hot working issues.

How Can We Correct It?

TME is irreversible, and its effects are permanent. By contrast, the effects of TE can be reversed. This is done by re-tempering above the critical temperature of 575°C (1070°F) then cooling rapidly. Impact toughness can be restored. If necessary, this process can be repeated.

A Simple Example

Alloy steel, which is susceptible to TE, will exhibit a relationship such as shown on Figure 2. Note that the impact toughness of quenched steel after tempering at 200−400°C (390−750°F) is lower than that obtained on tempering at temperatures below 200°C (390ºF). If brittle steel tempered in this range is heated above 400°C (750ºF) and transformed into a tough state, a second tempering at 250−400°C cannot return it to the brittle state. The rate of cooling from the tempering temperature range of 250−400°C has no effect on impact toughness.

Figure 2. Effect of temperature on impact toughness

The susceptibility of a given steel to TE depends on a number of factors, including grain size, hardness, steel grade, and the impurity control in the steelmaking process itself. Remember, not all steels and not all steelmaking processes are equivalent.

A heat treaters we must avoid the temptation to temper to a given hardness value without understanding the consequences of our actions. Since we do not have a simple embrittlement test that can be used on the shop floor, we must understand the phenomenon and question specifications that put us into TE ranges.

In Summary

The insidious nature of hydrogen embrittlement continues to cause concern and product failures during processing and during service, but as explained above, there are other heat treatment operations that can result in embrittlement. All of these and others (e.g., aluminum nitride embrittlement, overheating during forging, hot shortness) are responsible for many serious and in some instances catastrophic failures leading to injury or damage. All must be avoided.

References

ASTM International. 2022. ASTM B850-98 (Reapproved 2022): Standard Guide for Treatments of Steel for Reducing the Risk of Hydrogen Embrittlement. West Conshohocken, PA: ASTM International. https://www.astm.org.

Herring, D. H. 2014–2015. Atmosphere Heat Treatment, vols. 1–2. Troy, MI: BNP Media.

Herring, D. H. 2006. “The Embrittlement Phenomena in Hardened & Tempered Steels.” Industrial Heating, October.

Herring, D. H. 2004. “A Heat Treater’s Guide to Hydrogen Embrittlement.” Industrial Heating, October.

About the Author

Dan Herring
“The Heat Treat Doctor”
The HERRING GROUP, Inc.

Dan Herring has been in the industry for over 50 years and has gained vast experience in fields that include materials science, engineering, metallurgy, new product research, and many other areas. He is the author of six books and over 700 technical articles.

For more information: Contact Dan at dherring@heat-treat-doctor.com.

For more information about Dan’s books: see his page at the Heat Treat Store.

What Is Hydrogen Embrittlement? Part 2 Read More »

What Is Hydrogen Embrittlement? Part 1

/ BRAZING TECHNICAL CONTENT, Manufacturing Heat Treat Technical Content

Ask the Heat Treat Doctor® has returned to bring sage advice to Heat Treat Today readers and to answer your questions about heat treating, brazing, sintering, and other types of thermal treatments as well as questions on metallurgy, equipment, and process-related issues.

This informative piece was first released in Heat Treat Today’s September 2025 People of Heat Treat print edition.

If you’ve ever experience internal cracking, surface blistering, loss of ductility, or high pressure hydrogen attack, today’s Technical Tuesday might contain just the information you need to avoid it. Read below to learn from Dan Herring as he addresses what hydrogen embrittlement is, how to avoid it, and what solutions should not be pursued in order to fix it.

The other night, The Doctor decided to relax and watch a rather whimsical movie, The Great Race (1965), directed by Blake Edwards, who is perhaps better known for directing Breakfast at Tiffany’s and The Pink Panther. It is most memorable not for the actors, nor the plot, but for the infamous pie fight involving over 4,000 pies in a scene that took more than five days to film but lasted only four minutes on the big screen. Not one actor was spared the embarrassment of being hit by (multiple) pies in the face!

So, what does THIS have to do with heat treatment, you ask? Well, try as he may to believe the subject has been explained well in the past, The Doctor has been inundated recently with questions about hydrogen embrittlement (aka hydrogen-assisted cracking). Let’s learn more.

What Is It?

Hydrogen-assisted cracking (HAC) is an embrittlement phenomenon responsible for a surprising number of part cracking issues in heat treatment and is found to be the cause of many delayed field failures, especially if the components undergo secondary operations such as plating (Figure 1).

Figure 1. Tin-plated electrolytic tough pitch (ETP) copper battery lugs embrittled during oxy-acetylene brazing

How Does Hydrogen Get In?

It is generally agreed that hydrogen in atomic form will enter and diffuse through a metal surface at elevated or ambient temperatures. The simple rule to remember about hydrogen is fast in, slow out. Once absorbed, atomic hydrogen often combines to form molecular hydrogen or other hydrogen molecules (e.g., methane). As these are too large to diffuse through the metal, pressure builds at crystallographic defects (e.g., dislocations and vacancies) and/or discontinuities (e.g., voids, laps/seams, inclusion/matrix interfaces) causing minute cracks to form. Whether this absorbed hydrogen causes immediate cracking or not is a complex interaction of material strength, external stresses, and temperature.

Figure 2. Intergranular fracture of a plated component (SEM image)

Most heat treaters associate hydrogen embrittlement with the plating process and the lack of a proper bake-out cycle. However, there are many other sources of hydrogen, including heat treating atmospheres; breakdown of organic lubricants left on parts; the steelmaking process (e.g., electric arc melting of damp scrap); dissociation of high-pressure hydrogen gas; arc welding (with damp electrodes); grinding (in a wet environment); and the end-use environment.

Parts undergoing electrochemical surface treatments, such as etching, pickling, phosphate coating, corrosion removal, paint stripping, and electroplating, are especially susceptible (Figure 2).

What Is The Nature and Effect of Hydrogen Attack?

Although the precise mechanism(s) is the subject of active investigation (Figure 3), the reality is that components fail due to HAC. It is generally believed that all steels above 30 HRC are vulnerable, as are materials such as copper, titanium and titanium alloys, nickel and nickel alloys, and the like. See Table A below for examples of hydrogen damage and ways to avoid it.

Figure 3a and 3b. Hydrogen embrittlement mechanism models

Since a metallurgical interaction occurs between atomic hydrogen and the atomic structure, the ability of the material to elastically deform or stretch under load is inhibited. Therefore, it becomes “brittle” under applied stress or load. As a result, the metal will break or fracture at a much lower load or stress levels than anticipated by designers. Since failures can be of a delayed nature, hydrogen embrittlement is insidious.

Table A. Problems with hydrogen damage and ways to avoid them

In general, as the strength of the steel goes up, so does its susceptibility to hydrogen embrittlement. High strength steel, such as quenched and tempered steels (e.g., 4140, 4340), or precipitation hardened steels are particularly vulnerable. It is often called the Achilles heel of high strength ferrous steels and alloys.

Nonferrous Materials and Hydrogen Embrittlement

Nonferrous materials are also not immune to attack. Tough-pitch coppers and even oxygen-free coppers are subject to a loss of (tensile) ductility when exposed to reducing atmospheres. Bright annealing in hydrogen bearing furnace atmospheres or torch/furnace brazing are typical processes that can induce embrittlement of these materials.

In copper, the process involves diffusion and subsequent reduction of cuprous oxide (Cu₂O) to produce water vapor and pure copper. An embrittled copper often can be identified by a characteristic surface blistering resulting from expansion of water vapor in voids near the surface. Purchasing oxygen-free copper is no guarantee against the occurrence of hydrogen embrittlement, but the degree of embrittlement will depend on the amount of oxygen present. For example, CDA 101 (oxygen free electronic) allows up to 5 ppm oxygen while CDA 102 (OFHC) permits up to 10 ppm. A simple bend test is often used to detect the presence of hydrogen embrittlement. Metallographic techniques can also be used to look at the near surface and for the presence of voids at grain boundaries.

Are Low Hydrogen Concentrations Also Problematic?

Of concern today is embrittlement from very small quantities of hydrogen where traditional loss-of-ductility bend tests cannot detect the condition. This atomic level embrittlement manifests itself at levels as low as 10 ppm of hydrogen — in certain plating applications it has been reported that 1 ppm of hydrogen is problematic! Although difficult to comprehend, numerous documented cases of embrittlement failures with hydrogen levels this low are known.

This type of embrittlement occurs when hydrogen is concentrated or absorbed in certain areas of metallurgical instability. This concentrating action occurs via either residual or applied stress, which tends to “sweep” through the atomic structure, moving the infiltrated hydrogen atoms along with it. These concentrated areas of atomic hydrogen can coalesce into molecular type hydrogen, resulting in the formation of high localized partial pressures of the actual gas.

How Does Hydrogen Get Out?

Hydrogen absorption need not be a permanent condition. If cracking does not occur and the environmental conditions are changed so that no hydrogen is generated on the surface of the metal, the hydrogen can re-diffuse out of the steel, and ductility is restored. Performing an embrittlement relief cycle, or hydrogen bake-out cycle (the term “bake-out” is misleading as the process involves both inward diffusion and outgassing), is a powerful method in eliminating hydrogen before damage can occur. Key variables are temperature, time at temperature, and concentration gradient (atom movement).

Contact us with your Reader Feedback!

Electroplating, for example, provides a source of hydrogen during the cleaning and pickling cycles, but by far the most significant source is cathodic inefficiency. To eliminate concerns, bake-out cycles and recommended temperatures/times are shown in ASTM B850-98 (latest revision) as a function of steel tensile strength (see Table 1 of the specification). However, in this writer’s eyes, a “bake-out” cycle of at least 24 hours at temperature is required for the effective elimination of hydrogen as a concern regardless of the tensile strength of the material. Also, caution should be exhibited to prevent over-tempering or softening of the steel, especially on a carburized, or induction hardened part.

Next time we will talk about quench and temper embrittlement, as well as embrittlement due to overheating during forging, all of which are often mistaken for hydrogen embrittlement.

References

ASTM International. 2022. ASTM B850-98 (Reapproved 2022), Standard Guide for Treatments of Steel for Reducing the Risk of Hydrogen Embrittlement. West Conshohocken, PA: ASTM International. https://www.astm.org.

Herring, D. H. 2004. “A Heat Treater’s Guide to Hydrogen Embrittlement.” Industrial Heating, October.

Herring, D. H. 2006. “The Embrittlement Phenomena in Hardened & Tempered Steels.” Industrial Heating, October.

Herring, D. H. 2014–2015. Atmosphere Heat Treatment, Volumes I & II. Troy, MI: BNP Media.

Krause, George. 2005. Steels: Processing, Structure, and Performance. Materials Park, OH: ASM International.

About the Author

Dan Herring
“The Heat Treat Doctor”
The HERRING GROUP, Inc.

Dan Herring has been in the industry for over 50 years and has gained vast experience in fields that include materials science, engineering, metallurgy, new product research, and many other areas. He is the author of six books and over 700 technical articles.

For more information: Contact Dan at dherring@heat-treat-doctor.com.

For more information about Dan’s books: see his page at the Heat Treat Store.

Find Heat Treating Products And Services When You Search On Heat Treat Buyers Guide.Com

What Is Hydrogen Embrittlement? Part 1 Read More »

What Is Quench Cracking and How Can It Be Prevented?

/ Manufacturing Heat Treat Technical Content, QUENCHING TECHNICAL CONTENT

The Heat Treat Doctor® has returned to offer sage advice to Heat Treat Today readers and to answer your questions about heat treating, brazing, sintering, and other types of thermal treatments as well as questions on metallurgy, equipment, and process-related issues.

This informative piece was first released in Heat Treat Today’s August 2025 Automotive Heat Treating print edition.

Quench cracking during heat treatment can turn expensive components into scrap metal in seconds. In today’s Technical Tuesday article, Dan Herring (The Heat Treat Doctor®) explores more about the underlying mechanisms and proper preventative measures to save you time, money, and ensure reliable part performance.

As a young heat treater, I learned first-hand about quench cracking while running various dies for our tool and die shop — and succeeded in cracking all of them! I have never forgotten the foreman’s (rather animated) critique of my heat treating abilities. Quench cracking can be a significant problem for heat treaters, its potential consequences ranging from costly rework to premature failure in the field. Let’s learn more.

We must not only understand the mechanisms involved but also take proactive steps to avoid it. This includes careful consideration of such items as:

  • Material (e.g., chemistry, hardenability, form, mill processing)
  • Component part design (e.g., sharp radii, thin and thick sections next to one another)
  • Manufacturing processing steps (e.g., the effect of stress relief after rough machining)
  • Part loading (e.g., part orientation in relation to the quench, fixturing, total load weight)
  • Equipment choice (i.e., limitations and capabilities)
  • Quench medium (e.g., type, agitation, flow characteristics, temperature, temperature rise)
  • Process parameters (e.g., ramp rates, atmospheres, vacuum levels)

The Heat Treatment Challenge

Quench cracking primarily occurs during the hardening process, typically when materials are rapidly cooled via quenching. Since the cooling process introduces internal stresses within the material, it can result in crack formation. These stresses are a result of the rapid transformation of the material’s microstructure, most notably when transforming to martensite, a very hard, brittle structure.

Figure 1. Quench crack in a 4140 axle shaft

Mechanisms Involved

Failure mechanisms related to quench cracking include the following seven factors.

Material Imperfections

As material is heated, thermally induced stresses can cause existing surface or subsurface defects, such as inclusions, laps, and seams. These defects act as stress risers to open and propagate into cracks. Once a defect reaches “critical flaw size” — the smallest flaw that can lead to failure under expected operational stress levels — crack propagation will begin and lead to part failure.

Rapid or uneven heating only exacerbates this issue, especially when a material undergoes phase transformations that introduce volumetric changes.

Stress Risers

Sharp corners, steep edges around holes, and even grooves in parts create stress concentration points where quench cracking is most likely to occur. These features also result in localized heating and cooling, causing differential stresses that can initiate cracks.

  • The sharp edges of a part, for instance, cool much faster than the rest of the material, leading to a high risk of cracking.
  • Proper design modifications, such as adding radii to sharp corners, can reduce the likelihood of stress concentrations.

Rapid Cooling and Phase Transformation

The transformation from austenite to martensite during quenching is a key contributor to internal stresses. The rate at which the material cools can greatly influence these stresses. If cooling is too rapid or if tempering is delayed, the material can become overly brittle, leading to quench cracking.

Improper Heating and Overheating

Overheating during the austenitizing process can lead to coarse-grained structures that are more prone to quench cracking. Coarse grains increase the depth of hardening but reduce the material’s resistance to cracking. It is critical to avoid temperature overshoot, high ramp rates, and excessively long dwell times when heating.

Inadequate Quenching Methods

The choice of quench medium (brine, water, oil, polymer, high pressure gas, etc.) can also contribute to quench cracking. Overly aggressive quenchants may create excessive thermal stresses.

Improper Fixturing

The way parts are positioned during quenching can create problems. If parts are bunched together in a basket, uneven cooling rates will occur, with parts on the edges cooling faster than those in the center. This can lead to differential stresses and increase the risk of cracking.

Delays Between Quenching and Tempering

Quenching produces high residual stresses in the material, and if parts are not tempered soon after quenching, these stresses can lead to cracking. For materials with high hardenability, such as 4340 steel, immediate tempering (usually within 15 minutes of quenching) is critical to prevent in-service failure.

Understanding Fracture Mechanics

Contact us with your Reader Feedback!

Understanding these mechanisms is critically important. A material’s fracture toughness, which is the ability to resist crack growth, is defined by the stress intensity factor (KIC). This value varies based on the material’s properties and the size and geometry of the crack. The important point to remember is that when the applied stress reaches a critical threshold, cracks begin to propagate (literally at the speed of sound), leading to catastrophic failure.

Digging a bit deeper, there are three primary modes of fracture:

  • Tensile (Mode I): Fracture caused by tensile stress at the crack tip.
  • Sliding (Mode II): Fracture caused by shear stress that causes the two sides of the crack to slide.
  • Tearing (Mode III): Fracture caused by shear forces in a direction perpendicular to the crack plane.

Preventive Measures

Several strategies can be employed to minimize the risk of quench cracking during heat treatment. They broadly fall into the following categories.

Material Selection

Choosing the right material for the job is essential. Many designers select materials with high hardenability, forgetting that they can be prone to cracking. Additionally, one should take special care with materials that have high carbon content or are heavily alloyed.

Design Considerations

Ensure that part designs minimize stress risers. Avoid sharp corners and incorporate radii where necessary. Proper design can reduce the likelihood of cracks forming at critical locations.

Improved Manufacturing Practices

Proper stock removal during machining and addressing surface imperfections before heat treatment can prevent the initiation of cracks. Machining should aim to eliminate any seams or inclusions that might act as nucleation sites for cracks. Stress relief after rough machining is almost always a good idea.

Control of Heat Treatment Parameters

Maintain tight control over the heating and quenching processes to ensure uniformity. Avoid overheating and try to ensure that the part enters the quench medium in the best possible orientation to reduce the likelihood of creating differential cooling rates.

Figure 2. Quench crack due to a combination of rapid heating, overheating and improper polymer quench medium concentration in a motor shaft (50x, as polished)

Quenching Media

Select the appropriate quenching medium based on the material, part geometry, and load. Less aggressive quenchants or minimizing time in the quench should be considered for materials with moderate to high hardenability.

Post-Quench Tempering

Temper parts as soon as practical after quenching to avoid concerns with internal stresses. High-hardness materials should be tempered immediately to prevent quench cracking.

Quench Cracking in Other Materials

Quench cracking is not exclusive to steel. Other materials, such as nickel and cobalt superalloys, can also experience cracking due to similar mechanisms. In these materials, the phenomena are often referred to as “fire cracking,” “strain-age cracking,” or “stress cracking.” As with steel, cracks in these materials are often linked to high residual tensile stresses on the surface and the presence of stress raisers. Strategies, such as shot peening, redesigning part geometries, and improving surface finishes, can help mitigate cracking in superalloys.

Summing Up

Quench cracking represents a significant challenge in heat treatment, but by understanding its underlying mechanisms, heat treaters and engineers can take steps to mitigate the risk. Material selection, part design, proper heat treatment procedures, and timely tempering are all critical factors in preventing quench cracking and ensuring the integrity of components. A proactive approach to addressing flaws and stress concentrators combined with careful attention to detail in every stage of the manufacturing and heat treatment process can greatly reduce the likelihood of failure and contribute to the long-term success of heat treated products.

References

Herring, Daniel H. 2012. “Quench Cracking.” Industrial Heating, April.

Herring, Daniel H. 2015. Atmosphere Heat Treatment, Volume 2. BNP Media.

Johnson, D. D. 2005. “Thermal and Mechanical Behavior of Materials.” University of Illinois.

Klarstrom, Dwaine L. 1996. “Heat Treat Cracking of Superalloys.” Advanced Materials and Processes, April.

Krauss, George. 2005. Steels: Processing, Structure and Performance. ASM International.

About the Author

Dan Herring
“The Heat Treat Doctor”
The HERRING GROUP, Inc.

Dan Herring has been in the industry for over 50 years and has gained vast experience in fields that include materials science, engineering, metallurgy, new product research, and many other areas. He is the author of six books and over 700 technical articles.

For more information: Contact Dan at dherring@heat-treat-doctor.com.

For more information about Dan’s books: see his page at the Heat Treat Store.

Find Heat Treating Products And Services When You Search On Heat Treat Buyers Guide.Com

What Is Quench Cracking and How Can It Be Prevented? Read More »

Ask The Heat Treat Doctor®: What Are the Differences Between Intergranular Oxidation (IGO) and Intergranular Attack (IGA)? 

/ HARDENING TECHNICAL CONTENT, Manufacturing Heat Treat Technical Content

The Heat Treat Doctor® has returned to offer sage advice to Heat Treat Today readers and to answer your questions about heat treating, brazing, sintering, and other types of thermal treatments as well as questions on metallurgy, equipment, and process-related issues.

Today’s Technical Tuesday is a pre-release foretaste of the great content you can find in Heat Treat Today’s July 2025 Super Brands print edition.

Heat treaters and metallurgists speak a language unique to our industry and it can be confusing at times; terms like intergranular oxidation (IGO) and intergranular attack (IGA) are good examples, as these terms are often (incorrectly) used interchangeably. While these two phenomena sound similar, they have distinct mechanisms, causes, and impacts on material properties. Expert Dan Herring explores them more below.

What is IGO?  

Contact us with your Reader Feedback!

IGO is a process by which oxygen preferentially reacts with the metal surface at the grain boundaries, creating oxides (Figure 1). It is not uncommon, for example, to see IGO present after a hardening process run in an Endothermic or nitrogen/methanol atmosphere. As parts are heated to austenitizing temperature, oxygen present due to minute air leaks or produced during the various chemical reactions with the atmosphere results in IGO. The grain boundaries are highly susceptible to oxidation because these are areas where different crystallographic grains meet and are areas of high energy due to the atomic mismatch and disruption of the regular crystal lattice structure.  

Figure 1. Intergranular oxidation (IGO) along the surface of a heat treated chromium steel component. 1000X – As Polished
Source: The HERRING GROUP, Inc.

What is IGA?  

Figure 2. Intergranular attack (IGA) along the surface of a martensitic steel component caused by excessive submersion time in a citric acid solution. 1000X – As Polished
Source: The HERRING GROUP, Inc.

IGA, on the other hand, is a broader term that refers to a corrosion phenomenon (aka chemical attack) that specifically targets the grain boundaries of a material. Unlike IGO, intergranular attack (Figure 2) is not limited to oxidation reactions but encompasses a variety of forms of attack involving such things as the formation of precipitates, the dissolution of material at grain boundaries, or the creation of corrosion cracks. Common forms of IGA include stress corrosion cracking (SCC) or sensitization in stainless steel. 

In stainless steels, IGA is often triggered by high-temperature environments, usually in the range of 840º – 1560ºF (450 – 850°C) where carbon reacts with chromium to form chromium carbides at the grain boundaries, thus reducing the material’s resistance to corrosion in localized regions. In other alloys, factors like pH, chloride concentration, and temperature can lead to IGA. 

Both IGO and IGA weaken the material’s structural integrity or lead to embrittlement compromising the material’s integrity.

Effect on Material Properties 

The main effect of intergranular oxidation is the degradation of the mechanical properties, particularly a reduction in both ductility and toughness. As oxidation progresses along the grain boundaries, the material tends to become brittle, which can lead to premature failure under certain types of stress or thermal cycling. IGO often appears visually as a uniform discoloration or thin oxide layer on the surface. Surface pitting is not typically observed. 

By contrast, IGA often appears as visible cracks, pits, or localized regions where the metal has been attacked (along the grain boundaries). This leads to a reduction in mechanical strength and can lead to SCC under certain circumstances. IGA can severely compromise the integrity of the material, particularly in critical applications like pipelines, pressure vessels, and nuclear reactors.

Materials Involved 

IGO is most commonly observed in steel, aluminum, titanium, and nickel-based alloys, not only during heat treatment but when exposed to oxidizing environments in high-temperature applications, which also result in degradation and loss of material strength and other properties. 

IGA tends to be more prevalent in stainless steels, corrosion-resistant alloys, and aluminum alloys. It is especially noticeable in alloys that are susceptible to sensitization (where chromium carbides precipitate at grain boundaries), leading to localized corrosion and cracks. Alloys that form a passivating oxide layer can be more susceptible to IGA if that layer is disrupted. 

Principal Concerns 

The main concern with intergranular oxidation is material embrittlement, leading to reduced ductility and potential failure under mechanical stress, especially in high-temperature applications. It can also affect the integrity of critical components, such as those used in aerospace or power generation industries. 

By contrast, the primary impact of intergranular attack is loss of material strength, leading to structural failure, often without any clear outward signs (e.g., under chloride-induced SCC). It is more likely to cause immediate failure or a dramatic loss in performance, especially in structures exposed to corrosive environments. 

How to Detect IGO and IGA 

IGO is typically detected by examining the material’s surface using optical or scanning electron microscopy (SEM). Non-destructive techniques, such as X-ray diffraction (XRD), can also be used. 

IGA is usually detected through methods like microstructural examination, electrochemical testing, or failure analysis. Techniques, such as SEM or energy-dispersive X-ray spectroscopy (EDS), can be used to examine the grain boundary regions for signs of corrosion. 

How to Avoid IGO and IGA 

IGO can be avoided by one or more of the following: 

  • Environmental control: Making sure the heat treat furnace has no leaks, reducing oxygen partial pressure or controlling the furnace atmosphere in high-temperature heat treat operations. 
  • Alloy design: The use of materials with stable oxide-forming elements (e.g., chromium, titanium and aluminum) or alloys with high resistance to oxidation (e.g., nickel-based superalloys). 
  • Temperature control: Maintaining lower process temperatures and shorter times where possible to prevent oxidation at the grain boundaries. 
  • Coatings and surface treatments: Application of protective coatings, such as copper plating, post-heat treatment aluminizing, or chrome plating, to reduce oxygen interaction with the grain boundaries during service.  

IGA can be avoided by one or more of the following: 

  • Environmental control: Reducing exposure to aggressive chemicals (e.g., chloride ions) by maintaining proper pH levels or using inhibitors in post-cleaning processes. 
  • Proper alloy selection: Selecting materials resistant to intergranular corrosion (e.g., low carbon “L” grades of stainless steel or alloys with improved grain boundary stability). 
  • Heat treatment: Avoiding sensitization of stainless steel by proper heat treatment methods that prevent the formation of chromium carbides at grain boundaries. 
  • Stress relief: Reducing the likelihood of stress corrosion cracking by managing internal stresses during manufacturing and in-service conditions. 

Key Differences 

The differences between these phenomena are summarized in Table 1. 

Table 1. Key differences between IGO and IGA
Source: The HERRING GROUP, Inc.

Summing Up 

While both IGO and IGA involve attack at the grain boundaries, they differ in their mechanisms, causes, and effects. From a heat treater’s perspective, IGO most often results at high temperature in oxygen-bearing furnace atmospheres, while IGA often results from pre- or post-heat treatment processing (cleaning, passivation, plating, etc.). Proper material selection, furnace and environmental control, awareness of what can happen, and inspection for these effects are key to preventing them from occurring.  

References

Roberge, Pierre R., Corrosion Engineering: Principles and Practice, Mc-Graw Hill LLC, 2008.  

Stene, Einar S., Fundamentals of Corrosion: Mechanisms, Causes, and Monitoring.  

Schweitzer, Philip A., Fundamentals of Corrosion: Mechanisms, Causes and Preventative Methods, CRC Press, 2009. 

About the Author

Dan Herring
“The Heat Treat Doctor”
The HERRING GROUP, Inc.

Dan Herring has been in the industry for over 50 years and has gained vast experience in fields that include materials science, engineering, metallurgy, new product research, and many other areas. He is the author of six books and over 700 technical articles.

For more information: Contact Dan Herring at dherring@heat-treat-doctor.com.

For more information about Dan’s books: see his page at the Heat Treat Store.

Find Heat Treating Products And Services When You Search On Heat Treat Buyers Guide.Com

Ask The Heat Treat Doctor®: What Are the Differences Between Intergranular Oxidation (IGO) and Intergranular Attack (IGA)?  Read More »

Boronizing — What Is It and Why Is It Used?

/ Featured, HARDENING TECHNICAL CONTENT, Manufacturing Heat Treat Technical Content

The Heat Treat Doctor® has returned to offer sage advice to Heat Treat Today readers and to answer your questions about heat treating, brazing, sintering, and other types of thermal treatments as well as questions on metallurgy, equipment, and process-related issues.

This informative piece was first released in Heat Treat Today’s April 2025 Induction Heating & Melting print edition.

Of all the case hardening processes, boronizing (a.k.a. boriding) is perhaps the least understood and least appreciated. Let’s learn more.  

In this era of using coating technologies (e.g., PVD, CVD, DLC) to produce hard, wear-resistant surface layers on component parts, one often forgets that there is a thermo-chemical treatment that often can outperform many of them.  

Boronizing (a.k.a. Boriding)  

Table 1. Examples of hardness levels achieved by boronizing*
*The hardness of the boride layer depends on the compound formed. For example, FeB is 1900–2100 HV, Fe2B is 1800–2000 HV, while Ti2B is 3000 HV.

Boronizing is a case hardening process that produces a very high surface hardness in steels and is used for severe wear applications (see Table 1). The layer of borides (FeB and Fe2B) formed also significantly increases corrosion resistance of the steel.

Boron is added to steels for its unique ability to increase hardenability and lower the coefficient of (sliding) friction. In addition, boron is used to control phase transformation and microstructure since the time-temperature-transformation curve for the material when boron is diffused into the surface is shifted to the right. 

The Process

The boronizing process is typically run in a solid (pack), liquid, or gaseous medium. Each of these methods involves the diffusion of boron into the steel’s surface, but they differ in how boron is introduced and the conditions under which they operate. 

  • In the pack boronizing, a powder mixture of boron compounds (typically boron carbide or sodium tetrafluoroborate) is packed around the steel workpieces. This pack is placed in a retort-style furnace where it is heated, typically with an argon cover gas, to temperatures ranging from 1300°F to 1832°F (700°C to 1000°C). The heat causes the boron to diffuse into the steel surface, forming a boride layer (Figure 1). 
    • A key advantage of this method of boronizing is that it is highly effective for producing uniform boride coatings. It is particularly suitable for large parts or components that may not be suitable for immersion in a liquid or exposure to gaseous boron compounds. 
  • In liquid boronizing, the steel is immersed in a molten bath containing boron-bearing compounds, typically a mixture of sodium tetraborate and other chemicals. The steel absorbs boron from the bath, forming a boride layer. The liquid process tends to be faster than the solid method and can be more economical for certain applications. 
    • One of the challenges with liquid boronizing is that the process can be difficult to control in terms of coating thickness and uniformity. Therefore, this method is often used for smaller, simpler parts rather than large or complex geometries. 
  • Gaseous boronizing involves exposing the steel to a boron-containing gas, typically diborane (B2H6) or boron trifluoride (BF3), at elevated temperatures. The boron diffuses from the gas onto the surface of the steel, forming the boride layer. Gaseous boronizing allows for better control over the process compared to the other two methods, but it requires specialized equipment to handle the toxic and reactive nature of the boron gases. 
    • The advantage of gaseous boronizing lies in its ability to produce a uniform and controlled boride layer, especially for complex parts or those with intricate geometries. 

When working with any boron-containing compounds, adequate ventilation and other safety precautions (e.g., masks, gloves) are required. If boron tetrafloride is present, extra precautions are necessary since it is a poisonous gas.  

Typical processing temperature is in the range of 1300°F–1832°F (700°C–1000°C) with time at temperature from 1 to 12 hours. Typical case depths achieved range from 0.003″–0.015″ (0.076 mm to 0.38 mm) or deeper (Figure 2). Case depths between 0.024″ and 0.030″ require longer cycles up to 48 hours in duration. 

Figure 1. Typical microstructure of a boronized component

The mechanical properties of the borided alloys depend strongly on the composition and structure of the boride layers. The most desirable microstructure a er boronizing is a single-phase boride layer consisting of Fe2B2. Plain carbon and low alloy steels are good candidates for boronizing, while more highly alloyed steels may produce a dualphase layer (i.e., boron-rich FeB compounds) because the alloying elements interfere with boron diffusion. The boron-rich diffusion zone can be up to seven times deeper than the boride layer thickness into the substrate. 

The hardness of the borided layer depends on the composition of the base steel (Table 1). Comparative data on steels that have been borided versus carburized or carbonitrided, nitrided or nitrocarburized are available in the literature (see Campos-Silva and Rodriguez-Castro, “Boriding,” 651–702). The surface hardness achieved through boronizing is among the highest for case hardening processes. The boride layers typically exhibit hardness values in the range of 1000 to 1800 HV. This level of hardness helps prevent surface deformation under load, which is particularly beneficial in applications involving high contact pressures, such as gears, bearings, and automotive components. 

Contact us with your Reader Feedback!

Boronizing can also lower the coefficient of friction on the surface of the steel. This is particularly useful in applications where reduced friction is necessary, such as in sliding or rotating parts that operate under high pressures. The reduced friction helps to minimize wear and energy consumption, improving the overall efficiency and longevity of the components. 

Unlike other surface-hardening methods that can compromise the core properties of the material, boronizing tends to retain the toughness and ductility of the base steel. This means the steel remains strong and resistant to cracking or breaking while also benefiting from a hard, wear-resistant surface. 

By contrast, when boron is used as an alloying element in plain carbon and low alloy steels, it is added to increase the core hardenability and not the case hardenability. In fact, boron can actually decrease the case hardenability in carburized steels. Boron “works” by suppressing the nucleation (but not the growth) of proeutectoid ferrite on austenitic grain boundaries. Boron’s effectiveness increases linearly up to around 0.002% then levels off.  

Figure 2. Hardness-depth profiles on different borided steel*
* Notes:
1. The boriding temperature was 1740°F (950°C) with six (6) hours of exposure
2. Hardness conversion: 1 GPa = 102 HV (Vickers hardness)
3. Depth conversion: 10 micrometers = 0.00039 inches

Boronizing Applications 

Given the range of benefits that boronizing offers, it has found widespread use across many industries. Some of the most common applications include: 

  • Automotive industry: Gears, camshafts, and valve components are often boronized to enhance wear resistance and extend their service life. 
  • Aerospace: Parts exposed to high temperatures and wear, such as turbine blades, landing gears, and other critical engine components, benefit from the hard, wear-resistant coatings created by boronizing. 
  • Cutting tools and dies: The high surface hardness and resistance to abrasion make boronized tools highly effective for machining and forming hard materials. 
  • Mining and earthmoving equipment: Equipment like drill bits, shovels, and conveyor parts subjected to abrasive conditions can be boronized to improve their performance and reduce downtime. 
  • Oil and gas: Valves, pumps, and other equipment exposed to corrosive fluids in the oil and gas industry benefit from the enhanced corrosion resistance of boronizing. 

In Summary

Boronizing is not for everyone, but it is safe to say that it is the “forgotten” case hardening process, one that will find increasing use in the future as demand for better tribological properties increases. It is a highly effective surface treatment process that imparts significant benefits to steel, including enhanced wear and corrosion resistance, increased surface hardness, and improved frictional properties. By carefully selecting the boronizing method and optimizing process parameters, manufacturers can produce components with superior performance in demanding applications. As industries continue to push the boundaries of material performance, boronizing can be an essential technique for producing long-lasting, high-performance steel components.  

References

Campos-Silva. I. E., and G. A. Rodriguez-Castro, “Boriding to Improve the mechanical properties and corrosion resistance of steels.” In Thermochemical Surface Engineering of Steels, edited E. J. Mittemeijer and M. A. J. Somers. Woodhead Publishing, 2014. 

Herring, Daniel H. Atmosphere Heat Treatment, vol. I. BNP Media, 2014.  

Kulka, Michal. “Current Trends in Boriding: Techniques.” Springer Nature, 2019. 

Senatorski, Jan, Jan Tacikowski, and Paweł Mączyński. “Tribological Properties and Metallurgical Characteristics of Different Diffusion Layers Formed on Steel.” Inżynieria Powierzchni 24, no. 4 (2019).  

About the Author

Dan Herring
“The Heat Treat Doctor”
The HERRING GROUP, Inc.

Dan Herring has been in the industry for over 50 years and has gained vast experience in fields that include materials science, engineering, metallurgy, new product research, and many other areas. He is the author of six books and over 700 technical articles.

For more information: Contact Dan at dherring@heat-treat-doctor.com.

For more information about Dan’s books: see his page at the Heat Treat Store.

Find heat treating products and services when you search on Heat Treat Buyers Guide.Com

Boronizing — What Is It and Why Is It Used? Read More »

Métodos para la medición de la austenita retenida

/ AEROSPACE HEAT TREAT TECHNICAL CONTENT, QUENCHING TECHNICAL CONTENT

La mayoría de quienes aplican el tratamiento térmico reconocen la importancia de medir la austenita retenida (RA, por sus siglas en inglés); no obstante, muchos optan por no realizar estas mediciones por razones de tiempo y/o de los costos asociados. Este artículo explica los motivos por los cuales se deben practicar las mediciones RA, los factores a favor y en contra de las tecnologías de medición tradicionales y los beneficios de realizar la medición en la planta misma, utilizando tecnologías más avanzadas.

This informative piece was first released in Heat Treat Today’s March 2025 Aerospace Heat Treating print edition. To read the article in English, click here.

La importancia del porcentaje de austenita retenida

Antes de entrar a examinar algunas metodologías de medición, es necesario entender lo básico en relación a la austenita retenida, al igual que la importancia que reviste el porcentaje de la misma (%RA).

Austenita retenida (RA) es el nombre que se le da a la austenita que durante el proceso de templado no se transforma en martensita. En términos sencillos, la austenita retenida (figura 1) ocurre cuando el acero se ha templado sin llegar de manera contundente a la temperatura de acabado de la martensita (Mf); es decir, la temperatura ha estado por encima de lo requerido para permitir la formación de martensita al 100%. Debido a que la Mf está por debajo de la temperatura ambiente en la mayoría de las aleaciones que contienen más del 0.30% de carbón, se pueden presentar cantidades significativas de austenita retenida en la martensita a temperatura ambiente. (Herring, Atmosphere Heat Treatment).

Al tratarse del %RA, con frecuencia existe un equilibrio muy sensible entre sus efectos benéficos (el aumento en la durabilidad de ciertos componentes manufacturados) y sus atributos negativos (la creación de piezas susceptibles de fracturas y averías). Por tal motivo es de crítica importancia que los tratadores térmicos logren el %RA óptimo para la aplicación deseada.

Por ejemplo, en las industrias de la aeronáutica y la astronáutica, con frecuencia se especifica que los niveles de RA sean inferiores al 8%, y para piezas como los cojinetes y los actuadores lineales, se requiere un RA por debajo del 3%, lo más cercano posible a cero. No obstante, en otras aplicaciones, como por ejemplo los engranajes grandes para generadores de energía, energía eólica y plataformas de rendimiento, se ha identificado que un RA en el rango del 15-30% reviste mayores beneficios. (Errichello et al., “Investigations of Bearing Failures”). De igual manera, un alto % RA es una ventaja en el caso de cojinetes que vayan a entrar en contacto con lubricantes contaminados.

Figura 1. Microestructura en la superficie de la trayectoria de un cojinete de rodamiento 12CrNi3 (o SAE/AISI 9310) compuesto por martensita templada en la que se evidencia austenita retenida (áreas blancas)

Marco DeGasperi, gerente técnico de Verichek, se pronunció al respecto señalando que el %RA es de crítica importancia para los inyectores de combustible, para piezas pequeñas en aplicaciones médicas y para aplicaciones de alto nivel y alto volumen tales como las placas de desgaste en la industria minera. Lo resumió afirmando: –Cuando tu ejercicio se trate de someter a presión y movimiento cualquier dispositivo de calibración fina…si utilizas la palabra “precisión” para darte a conocer, vas a querer hacerte a una [herramienta de medición del %RA].

Las mismas características que le dan a la austenita retenida muchas de sus propiedades particulares, son a la vez las respons ables de significativos problemas de funcionamiento. Sabemos que la austenita es la fase normal del acero a altas temperaturas, mas no a temperatura ambiente. Debido a que la austenita retenida existe por fuera del rango normal de su temperatura, es metaestable, lo que quiere decir que, cuando entre en funcionamiento, los factores como la temperatura, el estrés, y aún el tiempo, harán que se transforme en martensita no revenida. Es más, junto con dicha transformación se dará un cambio en el volumen (aumentará) generando un alto grado de estrés interno en el componente y provocando muchas veces la formación de grietas lo que podrá llevar a que las piezas fallen en el campo.

El % RA también es importante, no solo por el impacto sobre la estabilidad dimensional, sino además por las propiedades mecánicas tales como el límite elástico, la resistencia a la fatiga, la tenacidad, y la manejabilidad. (Herring, Atmosphere Heat Treatment). A manera de ejemplo, DeGasperi identifica en la industria automotriz las consecuencias de un %RA demasiado alto o demasiado bajo: –Hablemos de las piezas en una transmisión o en una caja de transferencia; aquí es donde se dan los casos en los que se empiezan a romper los cojinetes, o terminas viéndote en la obligación del retiro masivo del producto del mercado. Y por lo general toda la cadena de suministro identifica al anterior como el culpable cuando ninguno en toda la cadena se ha tomado la molestia de probar las piezas por sí mismo.

Por el contrario, en algunos casos, la RA diseminada en pequeñas cantidades aporta para que el material resista la propagación de fracturas por fatiga y disminuye el estrés por fatiga en el contacto de rodamiento, así que lograr el correcto equilibrio en la cantidad de RA es importante en muchas aplicaciones. Además, el % justo de RA es esencial para el control de calidad, al igual que para evitar problemas de seguridad y retiros masivos del mercado. El debido control y la medición precisa del % RA en las aleaciones de acero es un punto crítico para garantizar la calidad y la seguridad de los componentes terminados, salvaguardando así la reputación y el margen de ganancia tanto de los tratadores térmicos como de los fabricantes.

Métodos de medición de RA

El medir con precisión la RA es de vital importancia para establecer si existe el balance correcto entre la austenita retenida y la martensita en determinado componente. Los tratadores térmicos tienen a su disposición varias metodologías para esta medición, cada una con sus respectivas ventajas y desventajas. Para el tratador térmico entender la importancia de medir el % RA representa tan solo una parte de la batalla ganada, mientras que la otra parte se gana cuando se logra identificar un método de medición que sea rápido, preciso y rentable.

La difracción de rayos-X: el mejor y más preciso de los métodos

Figura 2a. Una unidad de sobremesa ArexD de GNR

La difracción de rayos-X, utilizada para identificar y cuantificar las fases en un material, se considera el método más preciso de medición de RA en acero ya que logra establecer los niveles de RA hasta el rango aproximado de 0.5-1% (GNR, “AreX Diffractometer,” 3). En la difracción de rayos-X, las diferentes fases cristalinas demuestran diferentes patrones de difracción, lo que permite que sean identificadas y medidas. Además del análisis de fases, la difracción de rayos-X se puede utilizar para analizar car acterísticas microestructurales tales como la textura, el esfuerzo residual y el tamaño del grano.

Hoy en día, la difracción de rayos-X es una solución segura y no-destructiva que permite valorar una región mucho más amplia que la de varios de los otros métodos disponibles, sin necesidad de gran preparación ni análisis de la muestra, haciendo de ésta una solución más eficiente y efectiva. Es la tecnología más opcionada para una empresa que requiera valorar la RA con un resultado esperado inferior al 10%,

La actual generación de difractómetros de rayos-X ostenta un diseño de sobremesa con un peso aproximado de 25 libras. Existen modelos con costos inferiores a los USD $100.000, lo que los hace rentables frente al costo de un difractómetro tradicional (USD $200.000) que tenía además la desventaja de presentar dificultades cuando la muestra tuviera fases y reflexiones adicionales, ya fuera por el tamaño del grano, por los carburos o por las texturas que pudieran provocar disturbios y variaciones en la medición. La nueva generación de equipos de rayos-X logra superar estos obstáculos utilizando múltiples picos de difracción para minimizar los efectos de la orientación preferida y detectar la interferencia de los carburos.

Figura 2b. Una unidad de sobremesa ArexD de GNR

Las máquinas modernas de difracción de rayos-X tienen la capacidad de recoger hasta siete picos de difracción (tres para la fase ferrítica/martensítica y cuatro para la fase austenítica) para luego establecer la concentración de porcentaje por volumen de RA en la muestra al comparar las intensidades de los picos y analizar las relaciones entre éstos de acuerdo con el ASTM E975-22 (práctica estándar para la determinación por rayos-X de austenita retenida en acero con orientación cristalográfica cercana a la aleatoria).

No es complicado usar los equipos modernos de difracción de rayos-X. En menos de tres minutos se logra la medición con tan solo ubicar la muestra en la máquina y oprimir el botón de inicio. Estos difractómetros realizan mediciones en muestras de diferentes tamaños y se valen de software intuitivo, dando lugar a que cualquier técnico, tenga o no experiencia previa en metalurgia o difracción, efectúe la medición de manera rápida, precisa y eficiente.

La microscopía óptica: un método a prueba del tiempo

La RA se puede medir de manera metalográfica con un microscopio óptico. En la mayoría de los casos, un metalúrgico con experiencia puede establecer el %RA en el rango hasta del 10-15%, lo cual es más que suficiente para muchas aplicaciones, con el beneficio adicional de que también caracteriza la microestructura.

Este método, que implica establecer la fracción de austenita mediante el contraste derivado del comportamiento de grabado o morfología, es de bajo costo; sin embargo, puede ser demorado. En libros de referencia existen tablas y diagramas que ayudan a determinar el porcentaje de austenita retenida utilizando métodos comparativos. La microscopía óptica es subjetiva ya que depende del individuo y la interpretación que haga de la muestra bajo el microscopio.

Figura 3. Ejemplo de la técnica para medir los picos de %RA

Métodos alternos

Los tratadores térmicos también disponen de otros varios métodos de medición de la RA. Entre los más comunes se encuentran:

La inducción magnética: Aquí se magnetiza una muestra al punto de saturación y se mide la polarización de saturación. Con esto, se calcula la diferencia entre la saturación medida y la saturación teórica de la RA utilizando la ecuación.

La inducción magnética no es destructiva y ofrece un rango más alto y amplio que el de la microscopía óptica (1-30%). Sin embargo, al ser una medición de volumen, es necesario que el instrumento sea calibrado a los materiales específicos, junto con sus tratamientos térmicos y geometrías, lo cual exige mucho tiempo y depende en un alto grado de la habilidad del técnico.

Difracción de electrones por retrodispersión (EBSD, por sus siglas en inglés): Utilizar este método de medición de RA implica ubicar la muestra en un microscopio electrónico de barrido (SEM, por sus siglas en inglés) para caracterizar la estructura cristalográfica al igual que la microestructura. Las mediciones de RA con base en esta técnica no suelen ser muy precisas y dependen de la correcta preparación de la muestra. Adicionalmente, es un método destructivo y arroja una medida sobre un volumen muy pequeño.

En conclusión

El medir acertadamente el nivel de austenita retenida permite que tanto el ingeniero de diseño como el metalúrgico maximicen los efectos benéficos que ofrece, al mismo tiempo evitando sus consecuencias negativas. El tratador térmico, por su parte, deberá tener en cuenta la química del material y las variables del proceso de tratamiento térmico tales como la temperatura de austenización, la rapidez de enfriamiento, los tratamientos criogénicos o de congelación profunda y las temperaturas de templado.

Referencias

Errichello, Robert, Robert Budny, and Rainer Eckert. “Investigations of Bearing Failures Associated with White Etching Areas (WEAs) in Wind Turbine Gearboxes.” Tribology Transactions 56, no. 6 (2013): 1069–1076.

GNR, Analytical Instruments Group. “AreX Diffractometer: GNR Proposal for measuring Retained Austenite in the industrial domain and in laboratory.”

Herring, Daniel H., Atmosphere Heat Treatment. Volume I. Chicago: BNP Media, 2014.

Agradecimientos

Queremos agradecer a los siguientes contribuyentes por su aporte en el desarrollo de este artículo: Thomas Wingens, presidente y especialista en Heat Treat, WINGENS CONSULTANTS; Dennis Beauchesne, gerente general, ECM USA; Tim Moury, presidente & CEO, Marco DeGasperi, gerente técnico, Jeff Froetschel, vicepresidente y director financiero, Verichek Technical Services, Inc.; y Dan Herring, The Heat Treat Doctor®, The HERRING GROUP, Inc.

Find heat treating products and services when you search on Heat Treat Buyers Guide.Com

Métodos para la medición de la austenita retenida Read More »

Methods of Measuring Retained Austenite

/ AEROSPACE HEAT TREAT TECHNICAL CONTENT, QUENCHING TECHNICAL CONTENT

Most heat treaters recognize the importance of measuring retained austenite (RA), yet many opt not to perform these measurements due to time and/or cost constraints. This Technical Tuesday installment explains why performing RA measurements is necessary, the pros and cons of traditional measurement techniques, and the benefits of using more current and in plant technologies.

This informative piece was first released in Heat Treat Today’s March 2025 Aerospace Heat Treating print edition. To read the article in Spanish, click here.

Why Retained Austenite Percentage Matters

Before examining measurement methodologies, it is important to understand the fundamentals of retained austenite and why the percentage of retained austenite (RA%) matters.

Austenite that does not transform to martensite upon quenching is called retained austenite (RA). In simple terms, retained austenite (Figure 1) occurs when steel is not fully quenched to the martensite finish (Mf) temperature; that is, low enough to form 100% martensite. Because the Mf is below room temperature in most alloys containing more than 0.30% carbon, significant amounts of retained austenite may be present within the martensite at room temperature (Herring, Atmosphere Heat Treatment).

When it comes to RA%, there is often a delicate balance between its beneficial effects (an increase in the life of certain manufactured components) and its negative attributes (the creation of parts that are prone to cracking and failure). For this reason, it is crucial that heat treaters achieve the optimal RA% for the intended application.

For example, in the aeronautics and astronautics industries, RA levels are often specified to be under 8% and, for devices such as bearings and linear actuators, RA under 3% and as close to zero as possible is required. In other applications, however, such as large gearing for power generation, wind energy, and performance platforms, in the range of 15–30% or more RA has been found beneficial (Errichello et al., “Investigations of Bearing Failures”). Also, high RA% has been found beneficial for bearings that will be subjected to contaminated lubricants.

Figure 1. 12CrNi3 (similar to SAE/AISI 9310) bearing roller path surface microstructure consisting of tempered martensite with evidence of retained austenite (white areas)

Marco DeGasperi, technical manager at Verichek, weighed in on this, noting that for fuel injectors, small pieces in medical applications, and high-level, high-volume applications like wear plates in the mining industry, RA% is critical. He summarized with the statement, “When you’re applying pressure and motion to anything that’s fine-tuned … If you have ‘precision’ in your name, you probably want [an RA% measurement device].”

The very characteristics that give retained austenite many of its unique properties are those responsible for significant problems in service. We know that austenite is the normal phase of steel at high temperatures, but not at room temperature. Because retained austenite exists outside of its normal temperature range, it is metastable. This means that in service, factors such as temperature, stress, and even time will see it transform into untempered martensite. In addition, a volume change (increase) accompanies this transformation and induces a great deal of internal stress in a component, often manifesting itself as cracks, which leads to parts failing in the field.

RA% is also important not only because of its influence on dimensional stability but on mechanical properties such as yield strength, fatigue strength, toughness, and machinability (Herring, Atmosphere Heat Treatment). For example, looking in the automotive industry, DeGasperi gives an example of the consequences of having too high or too low RA%: “Let’s say pieces in a transmission or a transfer case; this is when gears start breaking or you get issued wide-end recalls. And then usually the supply chain all starts blaming the guy before them when nobody throughout the supply chain has actually tested the parts themselves.”

Alternatively, in some cases, finely dispersed RA helps the material resist the propagation of fatigue cracks and improves rolling contact fatigue stress, so balancing the amount of RA is important in many applications. Also, the correct RA% is essential for quality control, and proper control and accurate measurement of RA% in steel alloys is crucial to guaranteeing the quality and safety of finished components, as well as protecting the reputation and profitability of heat treaters and manufacturers.

RA Measurement Methods

Accurate RA measurements are critical to determine whether the correct balance of retained austenite and martensite exists within a given part. Several RA measurement methodologies are available to heat treaters, each having their own unique set of advantages and disadvantages. For heat treaters, understanding why it is crucial to measure the percentage of RA is only half the battle. Finding a cost-effective, fast, and accurate measurement method is the other half.

X-Ray Diffraction: The Best and Most Accurate Method

Figure 2a. An ArexD table-top unit from GNR

X-ray diffraction, which is used to identify and quantify phases in a material, is considered the most accurate method of RA measurement in steels as it can precisely determine RA levels down to the range of approximately 0.5–1% (GNR, “AreX Diffractometer,” 3). In X-ray diffraction, different crystalline phases have different diffraction patterns, allowing them to be identified and measured. In addition to phase analysis, X-ray diffraction can be used to analyze microstructural features such as texture, residual stress, and grain size.

Today, X-ray diffraction is a non-destructive, safe solution that can sample a much larger region than many other available methods and does not involve much sample preparation and analysis, making it a more efficient and effective solution. This is the option of choice for a company that needs to test RA with expected readings under 10%.

The current generation of X-ray diffractometers are tabletop sized, weighing about 25 lbs. With models under $100,000, they are also cost-effective when compared to traditional X-ray diffractometers ($200,000), which were sometimes problematic in the presence of additional phases and reflections due to grain size, carbides, or textures that could cause disturbances and variances in measurement. The new generation of X-ray equipment compensates for these obstacles via the use of multiple diffraction peaks to minimize the effects of preferred orientation and detect interference from carbides.

2b. An ArexD table-top unit from GNR

Modern X-ray diffraction machines can collect up to seven diffraction peaks (three for ferrite/martensite phase and four for austenite phase) and then determine the volume percent concentration of RA in the sample by comparing the intensities of the peaks and analyzing the peak ratios in accordance with the ASTM E975-22 (standard practice for X-ray determination of retained austenite in steel with near random crystallographic orientation).

The use of today’s X-ray diffraction equipment is not complicated. It can be measured in under three minutes by simply placing the sample in the machine and pressing the start button. These X-ray diffractometers measure various-sized samples and use intuitive software so the measurement can be performed quickly, accurately, and efficiently by any technician — with or without prior metallurgical or diffraction experience.

Optical Microscopy — A Time-Proven Method

RA can be measured metallographically with an optical microscope. An experienced metallurgist can usually determine RA% down to approximately 10–15% RA. For many applications, this is more than adequate and has the added benefit of characterizing the microstructure as well.

This method, which involves determining the austenite fraction using contrast from etching behavior or morphology, is low cost, however, it can be somewhat time consuming. Charts and diagrams in reference books are available to help determine the percentage of retained austenite by comparative methods. Optical microscopy is subjective as it is dependent upon the individual and their interpretation of the sample under the microscope.

Figure 3. Example of how RA% peaks are measured

Alternative Methods

Several other methods for measuring RA are available to heat treaters. The most common of these methods includes:

Magnetic Induction: Here, a sample is magnetized to saturation and the saturation polarization is measured. The difference between measured and theoretical saturation of the RA can then be calculated using this equation:

Magnetic induction is non-destructive and offers a higher, broader range than optical microscopy (1–30%). However, because it is a volume measurement, the instrument needs to be calibrated to the specific materials, heat treatment, and geometries, which is time consuming and highly dependent on the skill of the technician.

Electron Backscatter Diffraction (EBSD): Using this RA measurement method involves placing a sample in a Scanning Electron Microscope (SEM) to characterize the crystallographic structure as well as the microstructure. RA measurements using this technique are not particularly accurate and are reliant upon proper sample preparation. Additionally, it provides a very small measure volume and is a destructive test method.

Conclusion

Accurate measurement of the level of retained austenite allows both the design engineer and metallurgist to maximize its beneficial effects without suffering from its negative consequences. On the part of the heat treater this means taking into account the material chemistry and the heat treat process variables such as austenitizing temperature, quench rate, deep freeze or cryogenic treatments, and tempering temperatures.

References

Errichello, Robert, Robert Budny, and Rainer Eckert. “Investigations of Bearing Failures Associated with White Etching Areas (WEAs) in Wind Turbine Gearboxes.” Tribology Transactions 56, no. 6 (2013): 1069–1076.

GNR, Analytical Instruments Group. “AreX Diffractometer: GNR Proposal for measuring Retained Austenite in the industrial domain and in laboratory.”

Herring, Daniel H., Atmosphere Heat Treatment. Volume I. Chicago: BNP Media, 2014.

Acknowledgments

We’d like to thank the following contributors for the support of this article: Thomas Wingens, President & Heat Treat Specialist, WINGENS CONSULTANTS; Dennis Beauchesne, General Manager, ECM USA; Tim Moury, President & CEO, Marco DeGasperi, Technical Manager, Jeff Froetschel, VP & CFO, Verichek Technical Services, Inc.; and Dan Herring, The Heat Treat Doctor®, The HERRING GROUP, Inc.

This article is provided by the Heat Treat Today Editorial Team.

Find heat treating products and services when you search on Heat Treat Buyers Guide.Com

Methods of Measuring Retained Austenite Read More »

Skip to content